Compound of the abietene family



25 vol. 6, pages 638-640).

- Patented Oct. 17, 1933 UN lTEDI STA-ms;

' GOMPQUND or THE ssm'rsnnrmr Clyde 0. Henke, South Milwaukee, and Malcolm Charlton, Milwaukee, Wia, assignors,

II mesne assignments, to I. du'Pont' de Ne I I I mours &' Company, a corporation of Delaware No Drawings Application May 25 19 3 1 I I Serial'No.54 0,0 1 I 11 Claims; '(01. mam I This invention relates to novel compounds of the abietene family.

i More particularly this invention relatesto novel condensation products obtainable by reacting sulionic acids of the abietene family with aldehydes.

By the term sulionic acids of. hydrocarbons of the group consisting of abietene, abietine, and

abietane we mean the productsobtained by sulfonating a compound containing the abietene :IQ nucleus, such asabietene, abietine, or abietane.

The first two, abietene and abietine, are derivable by pyrogenic decomposition of rosin, abietic acid,

or abietyl chloride. Abietane is obtainable by hydrogenating abietene. Methods of preparing 15 these compounds as well as their sulfonation products, are described in the copending applicationg of Gubelmann and Henke Serial No. 431,626, filed Feb. 26, .1930, and in U. S. Patents Nos. 1,853,348, 1,853,352, and 1,853,353.;. However,

[ our invention is not limited to the particular derivatives obtainable by the particular methods disclosed in said copending applications. Many varietiesofabietene or abietine are known in the art, (see for instance, Ruzicka, Helv. Chim. Acta, The sulfonation products of anyof these derivatives, obtainable according to the above mentioned copending applications 'or according to any well known'method, are suit- I able for, our invention. t )0 We have now found that the above defined sulionic' acid compounds of the abietene, abietane andabietine hydrocarbons combine readily with aldehydes to give novel and useful, water-soluble compounds. The chemical nature of these comj pounds is not quite understood, but it is probable thatthey belongto the family of polyarylmethanes,rand are formed, for-example, according to the following equations: I x I j I 'Y'I abietcne-SQ;H

' 1 a apiece- -so,:i1-1-o=oHrcm- I a idem-:11

. abletene-SOaH abietene-SOaH I InEquation 2 "R stands for a hydrogen atom or an alkyl or aryl group. Our novel condensation products are, in the form of their free acids, soluble in water'and in benzene, but insoluble 56% sulfuric-aatcid. Upon evaporation from aibenzene solution they form a ack.pa y.; at a -t The fi tsw r quite stableand may be stored indefinitely with: outdecomposition. i I I The aldehyde condensation products, like the uncondensed. sulfonic acid derivatives of theabiew tene, abietine and abietane hydrocarbons, form excellent wetting, dispersing and tanning agents both in the form .of the free acids, or in the form of their alkali metal' salts. They are therefore very useful commercially both in thete'xtile and leather industries. Thus the addition of our novel compounds many aqueous treatment bath for textileflbers, forinstance in dyeing", bleach ing, securing and cleansing'flber, yarn or cloth, facilitates the penetration orthe fiber bythe liquid, improves the uniformityof the treatment, shortens the-{time of the treatment, and ingeneral increases theefliciency of the entire operation. 'Addition of these compounds to tanning baths-reduces the amount of natural tanning agent required, accelerates the time of tanning,

and improves the color and. texture of the'leather. I The preparation of ourjnovel products may be effected by dissolving the particular abietene,

abietine orl'abietane sulffonic acidbodyin 'concentrated, sulfuric acid and adding the particular The followingexamples will serve further ii-- lustrate our invention, I I I I ing'th'e same. vParts givenare parts by weight.

Example -1 I I II i. 1000 of sulfuric acid mo'nohydrate are placed in a sulfonation vessel fitted with an agitator, and cooled to about 10 C. 500 parts of abietene, such as for example, the" producfiobithout however, limits tained from grade Bor grade FF wood rosin, by heating the same at reflux temperatures until its acidity substantially disappears'as is more and the stirring is continued for about 2, hours.

The reaction mass is now poured into 1000 parts of water, stirred thoroughly, and allowed to settle. The lower, aqueous, acid-layer is discarded The upper layer, which contains the formaldehyde-abietene-sulfonic-acid condensation product is dissolved in water, neutralized with caustic soda, filtered, and evaporated to dryness. The

yield of the condensation mass is about 'l00parts.

If desired, instead of evaporating'the neutral-' ized filtration mass the latter may be extracted with benzene, and the extracted aqueous mass evaporated to dryness. tained' is considerably purer and better in its practical qualities than the product obtained without benzene extraction. The latter step apparently removes any residual unsulfonated 'oil. Instead of the 100 parts of a 40% formaldehyde solution above specified, 30 parts of paraformaldehyde'may be used, all other conditions remaining the same.- The product-is similar in properties to the product above described.

Example 2 The procedure is the same as in Example 1, except-that instead of 500 parts of abietene therein mentioned, 500 parts of abietane are used. The latter may be obtained by the hydrogenation of abietene in the presence of a catalyst as is more fully described and claimed in the copending ap plication of Gubelmann and Henke, Serial No. 431,626, filed Feb. 26, 1930. The .final product has substantially the same-properties as the product of Example 1, and like the product-oi Example 1 may be further improved by extracting its aqueous sodium salt solution with benzene;

} Example 3 110 parts of benzaldehyde are used instead of 100 partsof 40% formaldehyde as described in Example 1 and all the other details of Example 1 are maintained; The product is similar to that obtained in Example 1. It is evidently a condensation product of 2 mols of abietene and 1 mol of benzaldehyde.

Instead of using 110 parts benzaldehyde, 155 parts of benzal-chloride may be. used. In this case hydrochloric acid is liberated during the reaction, which either escapes as a gas or finds Example 4 I '28 parts of the benzene-extracted product ob.-

I compared to what would be required to produce The product thus ob- 3. The process of producing'water soluble com'-" pounds which comprises condensing sulfonic acids tained in Example lare dissolved in 84 parts of water. 448 parts of sumac extract are added, and the mixture is diluted with 1500 parts of water. 1000 parts of pickled sheepskin are now introduced, and the entire mass is agitated in a drum for about 3 to 4 hours. At the end of this period the sheepskin has become converted into leather of lighter color and better texture than leather obtainable by the use ofsumac extract alone. It will also be noted that the time required for tanning has been ,reducedfto about of that normally required when using sumac extract alone, and that the quantity of the sumac extract necessary has been reduced by about 20% the same tanning effect, if it were used alone.

The process of using our novel compounds in tanning is claimed in the copending application of Henke and Orthmann, Serial No. 540,009, filed of even.date herewith;

The tannin equivalent of our novel. condensation products, when determined by the American Leather Chemists Association method, runs about 40 to. 50% of the weight of the product.

I Other and further modifications may be in-'100 troduced in our invention without departing from the spirit of the same. i

Besides aldehydes in general, compounds which. react like aldehydes in condensation reactions may be used in our proces's'such as,'forexample, paraformaldehyde and benzal chlori'de. -We claim: r 1. The process of producing water soluble compounds which comprises condensing a sulfonic acid body of hydrocarbons of the group consist-f 110 ing of abietene, abietine and abietane with amember of the group consisting of aldehydes and compounds which reactlike aldehydes.

' 2. The process of producing water soluble compounds which comprises reacting a sulfonic acid body of ahydrocarbon selected fromjthe group consisting of abietene, abietine and abietane in concentrated sulfuric acid with a member of the group consisting of aldehydes and compounds which react like aldehydes.

of hydrocarbons of the group consisting of abietene, abietine and'abietane with formalde hyde.

4.- The process of producing'wate'r soluble com pounds which comprises condensing sulfonic acids of hydrocarbons of the group consisting of abietene, abietine and abietane with'benzaldehyde. 5; The process of producing water soluble compoundswhich comprises reacting upon a hydrocarbon of the group' consisting of abietene, abietine and.abietanewithsulfuric acid, adding a member of the group consisting ofaldehydes and compounds whichjreact like aldehydes to the sulfonation mass and recovering the reaction product.

6. A water. soluble condensation productof a sulfonic acid body of hydrocarbons selected from the group consisting of abietenej'abietineand abietane with a member of the group consisting of aldehydes and compounds which react like aldehydes. v

"l. A water soluble condensation product of sulfonic acids of hydrocarbons of the group consisting' of abietene, abietine and abietane with formaldehyde. l

'8. A water soluble condensation product of a sulfonic acid body of hydrocarbons selected from 3150 compounds which comprises condensing a sul- Ionic acid body of hydrocarbons selected from the group consisting of abietene, abietine'and abietane with benzal-chloride.

11. A water solublecondensation product of a suifonic acid body of hydrocarbons selected from- 1 the group consisting of abietene, abietine and abietane with benzal chioride. V

' CLYDE OQHENKE.

1 MALCOLM CHARLTON. 

